EP1477501A1 - Modified polymer and coating material - Google Patents
Modified polymer and coating material Download PDFInfo
- Publication number
- EP1477501A1 EP1477501A1 EP03737500A EP03737500A EP1477501A1 EP 1477501 A1 EP1477501 A1 EP 1477501A1 EP 03737500 A EP03737500 A EP 03737500A EP 03737500 A EP03737500 A EP 03737500A EP 1477501 A1 EP1477501 A1 EP 1477501A1
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- Prior art keywords
- modified polymer
- coating material
- coating
- polymer
- conjugated diene
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/04—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Definitions
- cyclized products of a conjugated diene polymer, and modified polymers thereof have heretofore been examined as ingredients for a coating liquid, an ink and an adhesive, which are applied for a polyolefin resin.
- a satisfactory improvement in adhesion is difficult or even impossible to achieve.
- a further improvement in adhesion is eagerly desired.
- a modified polymer having a hydroxyl value in the range of 1 to 100 mgKOH/g which is obtained by addition reaction of a compound (b) having one or more hydroxyl groups and a polymerizable unsaturated bond to a cyclized product (a) of a conjugated diene polymer having a cyclization degree in the range of 30 to 95%.
- a coating material comprising the above-mentioned modified polymer.
- An accelerated weathering test was carried out by exposing a coated shaped article to accelerated weathering for a predetermined time using a carbon-arc type sunshine weatherometer. Thereafter, specular reflection percentage was measured according to JIS K5400-7.6 at an incident angle of 60° from the light source.
- Flowability was determined by measuring flow-down time (in seconds) at 20°C by the Ford cup No.4 method according to JIS K 5400.
- Cyclization reaction was carried out by the same procedures as described in Example 1 wherein polyisoprene having a cis-1,4-structure isoprene content of 73%, a trans-1,4-structure isoprene content of 22% and a 3,4-structure isoprene content of 5%, and a weight average molecular weight of 107,000 was used, and the amount of p-toluenesulfonic acid was changed to 3.6 parts with all other conditions remaining the same.
- Modified polymer C was produced from the thus-obtained cyclized product solution, by the same procedures as described in Example 1 wherein the amount of 2-hydroxyethyl acrylate was changed to 5.6 parts with all other conditions remaining the same.
- the cyclization degree of cyclized product, and the weight average molecular weight and hydroxyl value of modified polymer C are shown in Table 1.
- Cyclization reaction of polyisoprene was carried out by the same procedures as described in Example 1 wherein the toluene solution containing the thus-obtained cyclized product was poured into 3,000 parts of a methanol solution containing 1% of 2,6-di-tert-butylphenol to recover a precipitate. The recovered precipitate was dried under a reduced pressure to obtain cyclized polymer F.
- the cyclization degree and weight average molecular weight of cyclized polymer F are shown in Table 1.
- the coating material comprising the modified polymer of the present invention exhibits improved adhesion to various shaped articles, particularly a resin shaped article, especially an olefin resin shaped article, and therefore, when the shaped articles are coated with the coating material, its surface appearance and texture can be kept for a long period of time.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A modified polymer having a hydroxyl value of 1 to 100
mgKOH/g, which is obtained by addition reaction of a compound
(b) having one or more hydroxyl groups and a polymerizable
unsaturated bond to a cyclized product (a) of a conjugated diene
polymer having a cyclization degree of 30 to 95%. A coating
material comprising this modified polymer is suitable as a primer
imparting enhanced adhesion, or a coating liquid or an ink
exhibiting enhanced adhesion, to various shaped articles,
especially an olefin resin shaped article.
Description
This invention relates to a modified polymer which is
obtained by modifying a cyclized product of a conjugated diene
polymer; and a coating material comprising the modified polymer.
It is known that isoprene rubbers such as natural rubber
and synthetic isoprene rubber are easily cyclized in the presence
of an acid catalyst. Several proposals have been made for
applying the thus-cyclized isoprene rubbers as a coating
material.
For example, a printing ink or a coating composition for
a polyolefin film or polyolefin shaped article has been proposed
in Japanese Unexamined Patent Publication No. S51-12827, which
ink or composition comprises a vehicle resin and optional
ingredients such as a plasticizer and a dispersant, wherein the
vehicle resin comprises a cyclized rubber obtained by cyclizing
using an acid catalyst a conjugated diene homopolymer or
copolymer having a low molecular weight. It is taught in this
patent publication that a coating having excellent adhesion and
crease-flex resistance can be obtained by using the cyclized
rubber as the vehicle.
Another proposal has been made in Japanese Unexamined
Patent Publication No. S53-142471, wherein it is taught that a
shaped article having a surface exhibiting enhanced adhesion and
capable of being easily subjected to fabrication such as coating,
printing and adhesion is obtained by modifying a surface of a
polyolefin resin shaped article with a surface-treating agent
comprising (i) a rubber ingredient selected from halogenated
polyolefin, halogenated rubber and cyclized rubber, and (ii) a
mixed solvent containing a terpene solvent.
A further proposal has been made in Japanese Unexamined
Patent Publication No. S57-145103, which describes a process for
producing a cyclized polymer wherein a specific low-molecular-weight
diene polymer is cyclized; said low-molecular-weight
diene polymer being a modified polymer obtained by addition
reaction of a low-molecular-weight isoprene polymer having a
molecular weight of 10,000 to 150,000 and containing at least
70% of cis-1,4 bond, wherein 0.3 to 12% by mole, based on the
isoprene monomer units in the isoprene polymer, of maleic
anhydride or a derivative thereof is added to the low-molecular-weight
isoprene. It is taught in this patent publication that
the thus-produced cyclized polymer exhibits enhanced adhesion
to and compatibility with a polyolefin resin and is suitable for
a printing ink and a coating material.
Thus, cyclized products of a conjugated diene polymer, and
modified polymers thereof, have heretofore been examined as
ingredients for a coating liquid, an ink and an adhesive, which
are applied for a polyolefin resin. However, in the case when
the hitherto proposed cyclized products and modified polymers
are incorporated as a binder or a vehicle in a coating liquid,
an ink or an adhesive, a satisfactory improvement in adhesion
is difficult or even impossible to achieve. Thus, a further
improvement in adhesion is eagerly desired.
In view of the foregoing state of prior art, a primary object
of the present invention is to provide a modified polymer capable
of giving a coating material such as a coating liquid, an ink
or a primer using the modified polymer, which exhibits enhanced
adhesion to various resins, especially polyolefin resins.
Another object of the present invention is to provide a coating
material exhibiting enhanced adhesion to various resins and resin
shaped articles.
The present inventors conducted extensive researches into
a method of modifying a cyclized product of a conjugated diene
polymer, and the amount of a modifying group to be included in
the cyclized product, and have found that the above-mentioned
objects can be achieved by a modified polymer having a specific
hydroxyl value, obtained by addition reaction of a compound
having one or more hydroxyl groups and a polymerizable
unsaturated bond, to a cyclized product of a conjugated diene
polymer.
Thus, in one aspect of the present invention, there is
provided a modified polymer having a hydroxyl value in the range
of 1 to 100 mgKOH/g, which is obtained by addition reaction of
a compound (b) having one or more hydroxyl groups and a
polymerizable unsaturated bond to a cyclized product (a) of a
conjugated diene polymer having a cyclization degree in the range
of 30 to 95%.
In another aspect of the present invention, there is
provided a coating material comprising the above-mentioned
modified polymer.
This coating material is suitable for producing a coated
shaped article by coating various shaped articles such as resin
shaped articles, especially a polyolefin resin shaped article,
with the coating material as, for example, a primer, a coating
liquid or an ink.
The modified polymer and coating material of the present
invention will be described in detail.
The modified polymer of the present invention is obtained
by addition reaction of a compound (b) having one or more hydroxyl
groups and a polymerizable unsaturated bond to a cyclized product
(a) of a conjugated diene polymer having a cyclization degree
in the range of 30 to 95%. The modified polymer must have a
hydroxyl value in the range of 1 to 100 mgKOH/g.
The cyclization degree of the cyclized product (a) of a
conjugated diene polymer is determined as follows. Peak area
of proton attributed to double bonds is measured before and after
the cyclization reaction of the conjugated diene polymer by
proton NMR, whereby the percentage of unreacted double bonds
remaining in the cyclized product, based on the double bonds in
the conjugated diene polymer as measured before cyclization, is
determined. The cyclization degree (%) is calculated by the
following formula:
Cyclization degree (%) = [100 - (% of unreacted double bonds
remaining in the cyclized product)]
The conjugated diene polymer used for the production of
the cyclized product (a) includes those which are prepared by
polymerization of a conjugated diene monomer by a conventional
procedure, and natural rubber. As specific examples of the
conjugated diene monomer, there can be mentioned 1,3-butadiene,
isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene,
1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene,
4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and
chloroprene. Of these, 1,3-butadiene and isoprene are
preferable. These conjugated diene monomers may be used either
alone or as a combination of at least two thereof.
The conjugated diene polymer giving the cyclized product
may be a copolymer of the conjugated diene monomer with other
copolymerizable monomer. As specific examples of the monomer
copolymerizable with the conjugated diene monomer, there can be
mentioned aromatic vinyl compounds such as styrene,
α-methylstyrene, p-methylstyrene, p-phenylstyrene,
p-methoxystyrene, chloromethylstyrene, m-fluorostyrene and
vinylnaphthalene; and olefinic compounds such as propylene,
isobutylene, vinyl chloride and vinylidene chloride. Of these,
aromatic vinyl compounds are preferable. Styrene and
α-methylstyrene are especially preferable.
The amount of the monomer copolymerizable with a
conjugated dine monomer is not particularly limited provided that
the effect of the present invention can be obtained, but, is not
more than 60% by weight, preferably not more than 45% by weight,
based on the total amount of the conjugated diene monomers.
The weight average molecular weight of the conjugated diene
polymer is not particularly limited, but is preferably in the
range of 30,000 to 500,000, more preferably 50,000 to 300,000,
as measured by GPC (gel permeation chromatography) and expressed
in terms of that of standard polystyrene. When the weight
average molecular weight is too small, the resulting modified
polymer tends to have a poor adhesion to a polyolefin resin. In
contrast, when the weight average molecular weight is too large,
a solution of the modified polymer is liable to have a high
viscosity and is often difficult to form a uniform coating
therefrom.
The cyclized product (a) of a conjugated diene polymer used
for the production of the modified polymer of the present
invention is produced by cyclizing the above-mentioned
conjugated diene polymer using an acid catalyst as cyclization
catalyst. More specifically the previously prepared conjugated
diene polymer is brought into contact with an acid catalyst in
an inert solvent.
As specific examples of the acid catalyst, there can be
mentioned sulfuric acid; sulfonic acids such as
monofluoromethanesulfonic acid, difluoromethanesulfonic acid
and p-toluenesulfonic acid, and anhydrides of these sulfonic
acids, and organic sulfonic acid compounds such as alkylesters
of these sulfonic acids; and metal halides such as boron
trifluoride, boron trichloride, tin tetrachloride, titanium
tetrachloride, aluminum chloride, diethylaluminum monochloride,
aluminum bromide, amtimony pentachloride, tungsten hexachloride
and iron chloride.
The inert solvent used as a reaction medium for cyclization
reaction is not particularly limited, and, as specific examples
thereof, there can be mentioned aromatic hydrocarbons such as
benzene, toluene, xylene and ethylbenzene; chain-like aliphatic
hydrocarbons such as n-pentane, n-hexane, n-heptane and
n-octane; and alicyclic hydrocarbons such as cyclopentane and
cyclohexane. Of these, hydrocarbons having a boiling point of
at least 70°C are preferable. The solvent used as polymerization
medium in the above-mentioned polymerization for the production
of a conjugated diene polymer can be used as it is as the reaction
medium for cyclization reaction. In this case, an acid catalyst
is added to the as-produced polymerization liquid to effect
cyclization of the conjugated diene polymer in the polymerization
liquid.
The reaction temperature, the reaction time, the amount
of acid catalyst, and other reaction conditions can appropriately
be determined depending upon the intended degree of cyclization.
The reaction temperature is preferably in the range of 20 to 200°C,
more preferably 50 to 150°C and especially preferably 80 to 100°C.
The reaction time is preferably in the range of 1 to 20 hours,
more preferably 2 to 15 hours and especially preferably 3 to 10
hours.
The cyclized product (a) of a conjugated diene polymer must
have a cyclization degree in the range of 30 to 95%. The
cyclization degree is preferably 50 to 90% and more preferably
55 to 85%. When the cyclization degree is too small or too large,
the object of the present invention is difficult to achieve. The
magnitude (n) of sequence of rings in the cyclized product (a)
is not particularly limited and n is usually in the range of 1
to 3.
The cyclized product (a) can be hydrogenated, if desired.
The manner for hydrogenation is not particularly limited. The
hydrogenation can be carried out in the conventional manner using
a conventional hydrogenation catalyst and hydrogen.
The modified polymer of the present invention is produced
by an additional reaction of a compound (b) having one or more
hydroxyl groups and a polymerizable unsaturated bond. The
compound (b) is not particularly limited provided that it has
one or more hydroxyl groups and a polymerizable unsaturated bond
and is capable of being added to the cyclized product (a) by heat
or a radical generator.
As specific examples of the compound (b), there can be
mentioned hydroxyalkyl esters of unsaturated acids such as
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
3-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
3-hydroxypropyl methacrylate and 2,3-dihydroxypropyl
methacrylate; unsaturated acid amides having a hydroxyl group
such as N-methylolacrylamide, N-(2-hydroxyethyl)acrylamide,
N-methylolmethacrylamide and N-(2-hydroxyethyl)-methacrylamide;
polyalkylene glycol monoesters such as
unsaturated acids such as polyethylene glycol monoacrylate,
polypropylene glycol monoacrylate, polytetramethylene glycol
monoacrylate, poly(ethylene glycol-propylene glycol)
monoacrylate, poly(ethylene glycol-tetramethylene glycol)
monoacrylate, poly(propylene glycol-tetramethylene glycol)
monoacrylate, polyethylene glycol monomethacrylate,
polypropylene glycol monomethacrylate, polytetramethylene
glycol monomethacrylate, poly(ethylene glycol-propylene
glycol) monomethacrylate, poly(ethylene glycol-tetramethylene
glycol) monomethacrylate and poly(propylene glycol-tetramethylene
glycol) monomethacrylate; and polyhydric
alcohol monoesters of unsaturated acids such as glycerol
monoacrylate and glycerol monomethacrylate. Of these,
hydroxyalkyl esters of unsaturated acids are preferable.
2-Hydroxyethyl acrylate and 2-hydroxymethyl methacrylate are
especially preferable.
The compounds (b) may be used either alone or as a
combination of at least two thereof.
The procedure of addition reaction by which the compound
(b) is added to the cyclized product (a) is not particularly
limited. Reaction conditions which are conventionally adopted
in ene-addition reactions or graft polymerization reactions can
be adopted. Usually the cyclized product (a) and the compound
(b) are heated in the presence or absence (solid phase reaction)
of a solvent and in the presence or absence of a radical generator
whereby the addition reaction can easily be effected.
The solvent used for the addition reaction includes, for
example, those which are used for the above-mentioned cyclization
reaction. The radical generator used for the addition reaction
includes, for example, peroxides such as di-tert-butyl peroxide,
tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide,
tert-butyl peroxybenzoate, methyl ethyl ketone peroxide and
di-tert-butyl diperphthalate; and azonitriles such as
azobisisobutyronitrile.
The thus-prepared modified polymer of the present
invention is comprised of a portion derived from the cyclized
product (a) and a portion derived from the compound (b). The
amount of hydroxyl group having been introduced into the cyclized
product (a) by the addition reaction is expressed in terms of
a hydroxyl value, i.e., amount (mg) of potassium hydroxide, as
determined by a method wherein 1 g of a modified polymer sample
is acetylized with an acetylating reagent, and the amount (mg)
of potassium hydroxide required for neutralizing the acetic acid
bound to the hydroxyl group is measured.
The modified polymer of the present invention must have
a hydroxyl value in the range of 1 to 100 mgKOH/g, preferably
5 to 50 mgKOH/g and more preferably 8 to 30 mgKOH/g. When the
hydroxyl value of modified polymer exceeds 100 mgKOH/g, a coating
material (e.g., a coating liquid) containing the modified polymer
tends to give a coating having a poor wet adhesion resistance.
In contrast, when the hydroxyl value is smaller than 1 mgKOH/g,
the coating material gives a coating having a poor adhesion.
The modified polymer usually has a weight average molecular
weight in the range of 5,000 to 600,000, preferably 20,000 to
400,000 and more preferably 35,000 to 300,000, as measured by
gel permeation chromatography (GPC) and expressed in terms of
that of polystyrene.
The manner of using the modified polymer of the present
invention, and the use thereof, are not particularly limited,
but the modified polymer is suitable for use in coating materials,
more specifically it is used as a binder resin or a vehicle resin
to be incorporated in various coating materials.
The coating material of the present invention comprises
the above-mentioned modified polymer, and is used for coating
at least part of the surface of a shaped article to make a coated
shaped article. The mode for use of the coating material is not
particularly limited, and, as preferable examples of the mode
for use, there can be mentioned a primer, a coating liquid and
an ink. These materials will be specifically described in the
following.
A primer is used as an undercoating material applied to
a surface to be coated prior to the application of other coating
materials such as a coating liquid or an adhesive. A primer is
a composition comprising a binder resin and optional ingredients,
which are uniformly dissolved or dispersed in a solvent. By using
the modified polymer of the present invention as a binder resin,
an adhesion between a surface of a shaped article and other coating
material can be enhanced.
The content of the modified polymer of the present
invention in a primer composition is not particularly limited,
but is usually in the range of 5 to 95% by weight, preferably
10 to 90% by weight and more preferably 15 to 80% by weight, based
on the weight of the primer composition. Other binder resins
may be incorporated in combination with the modified polymer of
the present invention in the primer composition. As specific
examples of the binder resins to be used in combination, there
can be mentioned an olefin resin, an acrylic resin, an urethane
resin, an epoxy resin, a melamine resin, an alkyd resin, a
chlorinated olefin rein, a silicone rubber and an acrylic rubber.
The ingredients optionally added in the primer composition
includes, for example, an antioxidant, an ultraviolet absorber,
a defoaming agent, a thickening agent, a dispersing agent and
a surface active agent.
The solvent used for the primer composition is not
particularly limited provided that a binder resin comprising the
modified polymer of the present invention can be dissolved or
dispersed therein. Ordinarily used solvents include an
aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent,
a ketone solvent, an alcohol solvent, an ether solvent, a halogen-containing
solvent and an aqueous solvent. Of these, an
aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent,
a ketone solvent and an aqueous solvent are preferable in view
of solubility of the binder resin and volatility of solvent.
No limitation is imposed to a coating liquid, an adhesive
or other coating materials to be coated on the primer-treated
surface of a shaped article. As preferable examples of the
coating liquid, there can be mentioned an acrylic coating liquid,
a polyester coating liquid, an alkyd-melamine coating liquid,
a polyurethane coating liquid and a polyester-melamine coating
liquid. As preferable examples of the adhesive, there can be
mentioned an epoxy adhesive, an urethane adhesive, an acrylic
adhesive an a cyanoacrylate rapidly curing adhesive.
A coating liquid usually comprises a pigment, a binder
resin, a solvent and optional ingredients. The binder resin has
a function of binding a pigment onto a surface of a shaped article.
When the modified polymer of the present invention is
incorporated as a binder resin in a coating liquid, a pigment
can be firmly adhered onto the shaped article surface. The amount
of the modified polymer of the present invention in the coating
liquid is not particularly limited, but is usually in the range
of 5 to 95% by weight, preferably 10 to 90% by weight and more
preferably 15 to 80% by weight, based on the weight of the coating
liquid.
Other binder resins may be incorporated in the coating
liquid in combination with the modified polymer of the present
invention, if desired. As specific examples of such binder
resins, there can be mentioned an acrylic resin, an urethane resin,
an epoxy resin, a melamine resin and an alkyd resin.
The pigment used for the coating liquid include, for
example, coloring pigments including organic pigments and
inorganic pigments, and rust-preventing pigments. The content
of pigment in the coating liquid may be appropriately determined
depending upon the particular kind of pigment, the intensity of
color, and other factors.
The solvent used for the coating liquid is not particularly
limited provided that a binder, a pigment and other ingredients
can be uniformly dissolved or dispersed therein. The solvent
used for the coating liquid include those which are used for the
above-mentioned primer composition. The ingredients optionally
added in the coating liquid includes, for example, an antioxidant,
an ultraviolet absorber, a defoaming agent, a thickening agent,
a dispersing agent and a surface active agent.
An ink usually comprises a coloring material, a vehicle
and optional ingredients. The modified polymer of the present
invention is especially useful as a vehicle for an ink, especially
gravure ink.
A vehicle has a function of bonding a coloring material
onto a surface of a shaped article, and usually comprises a polymer
ingredient and a solvent. The modified polymer of the present
invention is contained in the polymer ingredient in an amount
of 5 to 100% by weight, preferably 10 to 90% by weight and more
preferably 20 to 80% by weight, based on the weight of the polymer
ingredient. The polymer ingredient in the vehicle may comprise
other polymers in combination with the modified polymer of the
present invention, and, as examples of such polymers, there can
be mentioned those which are mentioned above as binder resins
to be optionally incorporated in the primer composition.
A coloring material used for an ink includes, for example,
pigments including organic pigments and inorganic pigments, and
carbon black and dyes. Of these, pigments are preferable in view
of the light resistance and chemical resistance.
The solvent used for the ink is not particularly limited
provided that the polymer ingredient, a coloring material and
other optional ingredients can be uniformly dissolved or
dispersed therein. The solvent used for the ink includes organic
solvents and aqueous solvents, and, as specific examples thereof,
there can be mentioned those which are used for the
above-mentioned primer composition.
The ingredients optionally added in the ink includes, for
example, a plasticizer, a dispersing agent, a defoaming agent,
a leveling agent, a viscosity-modifier, an adhesion-imparting
agent, an antistatic agent and a filler. A polymerizable monomer,
a curing agent, a defoaming agent or a reaction initiator may
be incorporated in the ink to give an ink curable with ultraviolet
rays or by heat, and having a more enhanced adhesion.
Shaped articles to be coated with the above-mentioned
coating material are not particularly limited, but are preferably
various resin shaped articles, and especially preferably
polyolefin resin shaped articles. As specific examples of the
polyolefin resin, there can be mentioned propylene resins such
as a propylene homopolymer, a propylene-ethylene copolymer, a
propylene-butene copolymer and a propylene-octene copolymer; an
ethylene homopolymer; norbornene polymers and hydrogenation
products thereof; and cyclic conjugated diene polymers and
hydrogenation products thereof.
The procedure for coating shaped articles with the
above-mentioned coating material to give a coated shaped article
is not particularly limited. The amount of coating material to
be applied onto the shaped article is also not particularly
limited, but is usually chosen in the range of 1 to 100 µm as
expressed in terms of thickness of dry coating. The coating can
be carried out by the conventional procedure including, for
example, spray coating, brush coating, trowel coating, roll
coating, flow-coating and dip coating. The liquid coating
material applied can be dried at room temperature or under heated
conditions.
The invention will now be specifically described by the
following examples that by no means limit the scope of the
invention.
Parts and % in the following examples are by weight unless
otherwise specified.
The weight average molecular weight of polymers was
measured by gel permeation chromatography (GPC) and expressed
in terms of that of standard polystyrene.
Cyclization degree of a cyclized product of a conjugated
diene polymer was determined as follows. Peak area of proton
attributed to double bonds is measured before and after the
cyclization reaction of the conjugated diene polymer by proton
NMR, whereby the percentage of unreacted double bonds remaining
in the cyclized product, based on the double bonds in the
conjugated diene polymer as measured before cyclization, is
determined. The cyclization degree (%) is calculated by the
following formula:
Cyclization degree (%) = [100 - (% of unreacted double bonds
remaining in the cyclized product)]
Hydroxyl value (mgKOH/g) of a modified polymer was
determined according to the method described in "Standard Methods
for the Analysis of Oils and Fats and Derivatives" 2.4.9.2-83,
published by Japan Oil Chemists' Society.
A coated surface of a resin shaped article was scored by
drawing eleven scored lines with 2 mm intervals in each of the
two directions perpendicular to each other by a cutter to form
a lattice pattern having 100 squares. A self-adhesive cellophane
tape was adhered on the lattice pattern, and a peeling test was
conducted by pulling the adhered tape rapidly at a peeling angle
of 45°. The initial adhesion was evaluated by the ratio in % of
the number of squares remaining without separation per 100
squares.
A coated resin plate was dipped in warm water maintained
at 40°C for 240 hours. Thereafter, a lattice pattern cutting test
was conducted in the same manner as mentioned above for the
determination of the initial adhesion. The wet adhesion was
evaluated by the ratio in % of the number of squares remaining
without separation per 100 squares.
An accelerated weathering test was carried out by exposing
a coated shaped article to accelerated weathering for a
predetermined time using a carbon-arc type sunshine
weatherometer. Thereafter, specular reflection percentage was
measured according to JIS K5400-7.6 at an incident angle of 60°
from the light source.
Flowability was determined by measuring flow-down time (in
seconds) at 20°C by the Ford cup No.4 method according to JIS
K 5400.
Ink-coated surface of a shaped article was superposed upon
another ink-coated surface of a shaped article so that the
ink-coated surfaces are contacted with each other. The
superposed ink-coated surfaces are pressed at a temperature of
110°C under a pressure of 9.8 × 10-2 MPa for 2 seconds to be thereby
heat-sealed, and then the heat-sealed articles were allowed to
stand at a temperature of 23°C for 24 hours in a thermostatic
chamber. Then a peeling test was carried out at a pulling rate
of 50 mm/min and a peeling angle of 180° to measure heat-sealing
strength (g/cm).
A four-necked flask equipped with a stirrer, a thermometer,
a reflux condenser and a nitrogen gas-introducing tube was
charged with 100 parts of polyisoprene (cis-1,4-structure
isoprene content: 86%, trans-1,4-structure isoprene content: 12%,
3,4-structure isoprene content: 2%; weight average molecular
weight: 136,000), and 1,570 parts of toluene. The polyisoprene
was cut into squares having a size of 10 mm × 10 mm prior to the
introduction into the flask. The inner atmosphere of the flask
was substituted by nitrogen gas, and then the flask was placed
in an oil bath maintained at 85°C while the content was stirred,
whereby polyisoprene was dissolved in toluene. After completion
of dissolution, 3.9 parts of p-toluenesulfonic acid were added,
and the mixed solution was stirred while being maintained at 85°C,
to conduct a cyclization reaction. When 5 hours elapsed, 400
parts of ion-exchanged water were added to the reaction liquid
to stop the cyclization reaction. The reaction liquid was
allowed to stand for 30 minutes to separate an oil layer. The
separated oil layer was washed three times with 400 parts of
ion-exchanged water, and thereafter was subjected to centrifugal
separation at a revolution number of 300 rpm to remove water.
Then the oil layer was heated at 130°C to completely remove water.
To the solution in toluene of the thus-obtained cyclized
product, 10.0 parts of 2-hydroxyethyl methacrylate was added at
a constant rate over a period of 5 minutes while the toluene
solution was stirred. After an addition reaction was conducted
at 160°C for 4 hours, the reaction liquid was poured into a 3,000
parts of a methanol solution containing 1% of
2,6-di-tert-butylphenol to recover a precipitate. The
recovered precipitate was dried under a reduced pressure to
obtain modified polymer A. The cyclization degree of cyclized
product, and the weight average molecular weight and hydroxyl
value of modified polymer A are shown in Table 1.
Cyclization reaction was carried out by the same procedures
as described in Example 1 wherein polyisoprene having a
cis-1,4-structure isoprene content of 73%, a trans-1,4-structure
isoprene content of 22% and a 3,4-structure isoprene content of
5%, and a weight average molecular weight of 107,000 was used,
and the amount of p-toluenesulfonic acid was changed to 3.6 parts
with all other conditions remaining the same.
Modified polymer B was produced from the thus-obtained
cyclized product solution, by the same procedures as described
in Example 1 wherein the amount of 2-hydroxyethyl acrylate was
changed to 4.0 parts with all other conditions remaining the same.
The cyclization degree of cyclized product, and the weight
average molecular weight and hydroxyl value of modified polymer
B are shown in Table 1.
Cyclization reaction was carried out by the same procedures
as described in Example 1 wherein polyisoprene having a
cis-1,4-structure isoprene content of 28%, a trans-1, 4-structure
isoprene content of 14% and a 3,4-structure isoprene content of
56%, and a weight average molecular weight of 252,000 was used,
and the amount of p-toluenesulfonic acid was changed to 3 parts
with all other conditions remaining the same.
Modified polymer C was produced from the thus-obtained
cyclized product solution, by the same procedures as described
in Example 1 wherein the amount of 2-hydroxyethyl acrylate was
changed to 5.6 parts with all other conditions remaining the same.
The cyclization degree of cyclized product, and the weight
average molecular weight and hydroxyl value of modified polymer
C are shown in Table 1.
Cyclization reaction was carried out by the same procedures
as described in Example 1 wherein polybutadiene having a
cis-1,4-structure butadiene content of 26%, a
trans-1,4-structure butadiene content of 18% and a 1,2-structure
butadiene content of 56%, and a weight average molecular weight
of 210,000 was used instead of polyisoprene, and the amount of
toluene was changed to 1,620 parts. Further, after the
polybutadiene was completely dissolved in toluene, the solution
was maintained at 23°C, 2.78 parts of benzyl chloride and 1.98
parts of ethylaluminum chloride were added instead of
p-toluenesulfonic acid. When 12 minutes elapsed from the
dissolution, 20 parts of methanol were added to the reaction
liquid to stop the cyclization reaction. All other conditions
remained the same.
Modified polymer D was produced from the thus-obtained
cyclized product solution, by the same procedures as described
in Example 1 wherein 3.0 parts of 2-hydroxyethyl methacrylate
were added to conduct an addition reaction with all other
conditions remaining the same. The cyclization degree of
cyclized product, and the weight average molecular weight and
hydroxyl value of modified polymer D are shown in Table 1.
In this comparative example, a maleic acid-modified
polymer was produced by reference to the procedures as described
in Japanese Unexamined Patent Publication No. 57-145,103.
A four-necked flask equipped with a stirrer, a thermometer,
a reflux condenser and a nitrogen gas-introducing tube was
charged with 100 parts of polyisoprene (cis-1,4-structure
isoprene content: 73%, trans-1,4-structure isoprene content: 22%,
3,4-structure isoprene content: 5%; weight average molecular
weight: 107,000), and 1,570 parts of toluene. The polyisoprene
was cut into squares having a size of 10 mm × 10 mm prior to the
introduction into the flask. The inner atmosphere of the flask
was substituted by nitrogen gas, and then the flask was placed
in an oil bath maintained at 80°C while the content was stirred,
whereby polyisoprene was dissolved in toluene. After completion
of dissolution, 7.2 parts of maleic anhydride were added, and
the mixed solution was stirred while being maintained at 80°C,
to conduct a cyclization reaction. After an addition reaction
was conducted for 1 hour, the reaction liquid was poured into
a 3,000 parts of a acetone solution containing 1% of
2,6-di-tert-butylphenol to recover a precipitate. The
recovered precipitate was dried under a reduced pressure to
obtain a maleic acid-modified isoprene polymer.
100 parts of the maleic acid-modified isoprene polymer was
dissolved in 300 parts of toluene. To the obtained solution,
3.6 parts of p-toluenesulfonic acid were added and the solution
was maintained at 85°C to conduct a cyclization reaction with
stirring. When about 5 hours elapsed, 400 parts of ion-exchanged
water were added to the reaction liquid to stop the cyclization
reaction. The reaction liquid was allowed to stand for 30 minutes
to separate an oil layer. The separated oil layer was washed
three times with 400 parts of ion-exchanged water, and thereafter,
the oil layer was poured into a 1, 000 parts of a methanol solution
containing 1% of 2,6-di-tert-butylphenol to recover a
precipitate. The recovered precipitate was dried under a reduced
pressure to obtain a cyclized product of the maleic acid-modified
isoprene polymer (modified polymer E). The cyclization degree
and weight average molecular weight of modified polymer E, and
the amount of maleic anhydride added in modified polymer E are
shown in Table 1.
Cyclization reaction of polyisoprene was carried out by
the same procedures as described in Example 1 wherein the toluene
solution containing the thus-obtained cyclized product was
poured into 3,000 parts of a methanol solution containing 1% of
2,6-di-tert-butylphenol to recover a precipitate. The
recovered precipitate was dried under a reduced pressure to
obtain cyclized polymer F. The cyclization degree and weight
average molecular weight of cyclized polymer F are shown in Table
1.
Cyclization reaction of polyisoprene was carried out by
the same procedures as described in Example 1, and then, modified
polymer G was produced from the thus-obtained cyclized product
solution, by the same procedures as described in Example 1 wherein
the amount of 2-hydroxyethyl acrylate was changed to 36.3 parts
with all other conditions remaining the same. The cyclization
degree of cyclized product, and the weight average molecular
weight and hydroxyl value of modified polymer G are shown in Table
1.
| Examples | Comparative Examples | ||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | |
| Modified | |||||||
| polymer | A | B | C | D | E | F | G |
| CD (%) of | |||||||
| cyclized | 83 | 78 | 71 | 58 | 82 | 83 | 83 |
| product | |||||||
| Mw of | |||||||
| cyclized | 95,200 | 73,000 | 252,000 | 179,000 | 75,000 | 95,400 | 95,400 |
| product | |||||||
| OH value | 28.5 | 16.9 | 11.2 | 8.1 | - | - | 140 |
| (mgKOH/g) | |||||||
| Amount of | |||||||
| maleic | |||||||
| anhydride | - | - | - | - | 3.1 | - | - |
| added (wt.%) |
Seven kinds of primers were prepared by using modified
polymers A through G as binder resins, produced in Examples 1-4
and Comparative Examples 1-3, according to the formulations
(parts by weight) shown in Table 2. The ingredients shown in
Table 2 were mixed together by a high-speed stirrer (Disper) for
10 minutes, and each mixture was diluted with toluene to give
a primer having a flowability of 13 to 14 seconds as flowing down
time.
| Examples | Comparative Examples | ||||||
| 5 | 6 | 7 | 8 | 4 | 5 | 6 | |
| Modified | |||||||
| polymer A | 10 | - | - | - | - | - | - |
| Modified | |||||||
| polymer B | - | 10 | - | - | - | - | - |
| Modified | |||||||
| polymer C | - | - | 10 | - | - | - | - |
| Modified | |||||||
| polymer D | - | - | - | 10 | - | - | - |
| Modified | |||||||
| polymer E | - | - | - | - | 10 | - | - |
| Modified | |||||||
| polymer F | - | - | - | - | - | 10 | - |
| Modified | |||||||
| polymer G | - | - | - | - | - | - | 10 |
| Titanium | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| oxide | |||||||
| Carbon | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| black | |||||||
| Toluene | 85 | 85 | 85 | 85 | 85 | 85 | 85 |
Resin materials shown in Table 3 were mixed together by
Henschel mixer and melt-kneaded by a twin-screw extruder to
produce pellets. The pellets were injection-molded to give three
kinds of plates X, Y and Z each having a size of 50 mm × 80 mm
× 3 mm.
| Plate molding | Resin material and ingredients for plate molding |
| X | Polypropylene resin, J-3054HP available from |
| Idemitsu Petro. Chem. Co. | |
| Y | Hydrogenated product of ring-opened polymer |
| comprising 15 wt.% of ethyltetracyclododecene | |
| units and 85 wt.% of dicyclopentadiene units. | |
| Tg: 103°C, degree of hydrogenation: more than 99%. | |
| Z | (1) Polypropylene resin, J-3054HP available from |
| Idemitsu Petro. Chem. Co. | |
| (2) Ethylene/butane-1 copolymer, EBM 3021 | |
| available from JSR Corporation | |
| (3) Talc JM-209, available from Asada Seifun K.K. | |
| Ratio (1)/(2)/(3) = 70/23/7 (parts by weight) |
Plates X, Y and Z were washed thoroughly with water, and
then dried. A primer having the formulation shown in Table 2
was applied onto each plate by a spray coating method at a spraying
pressure of 3.5 to 5.0 MPa using a spray gun with an orifice of
1.0 mm diameter to form a coating having a thickness of 10 µ
m. When 5 minutes elapsed, a two-part curable urethane metallic
coating liquid (tradename "RB-212" base coating liquid and
tradename "RB-288" clear coating liquid, available from Nippon
Bee Chemical Co., Ltd.) was applied by a two-coat method using
the same spray gun as mentioned above to form a coating having
a thickness of 40 µm. Then drying was carried out at 23°C for
15 minutes and further at 80°C for 30 minutes in a non-circular
drier. The dried coated plate was allowed to stand for 3 days
at room temperature, and then, was tested for its initial adhesion
(lattice pattern cutting test) and wet adhesion. The results
of initial adhesion test and wet adhesion test are shown in Tables
4 and 5, respectively.
| Plate X | Plate Y | Plate Z | |
| Example 5 | 100/100 | 100/100 | 100/100 |
| Example 6 | 100/100 | 100/100 | 100/100 |
| Example 7 | 100/100 | 100/100 | 100/100 |
| Example 8 | 100/100 | 100/100 | 100/100 |
| Comp. Ex. 4 | 50/100 | 60/100 | 50/100 |
| Comp. Ex. 5 | 0/100 | 0/100 | 20/100 |
| Comp. Ex. 6 | 40/100 | 50/100 | 70/100 |
| Plate X | Plate Y | Plate Z | |
| Example 5 | 100/100 | 100/100 | 100/100 |
| Example 6 | 100/100 | 100/100 | 100/100 |
| Example 7 | 100/100 | 100/100 | 100/100 |
| Example 8 | 100/100 | 100/100 | 100/100 |
| Comp. Ex. 4 | 40/100 | 30/100 | 60/100 |
| Comp. Ex. 5 | 0/100 | 0/100 | 0/100 |
| Comp. Ex. 6 | 0/100 | 0/100 | 0/100 |
As seen from the evaluation results shown in Tables 4 and
5, in the case when a resin shaped article is pre-coated with
a primer having incorporated therein each of modified polymers
A through D of the present invention, a coating formed on the
primer undercoating layer exhibits greatly improved adhesion.
In contrast, in the case when a resin shaped article is pre-coated
with a primer having incorporated therein a maleic anhydride-modified
polymer E, an unmodified cyclized polymer F or a modified
polymer G having a too large hydroxyl value, a coating formed
on the primer undercoating layer exhibits poor adhesion.
A four-necked flask equipped with a stirrer, a thermometer,
a reflux condenser and a nitrogen gas-introducing tube was
charged with 800 parts of terephthalic acid, 770 parts of
2-butyl-2-ethyl-1,3-propanediol, 72.7 parts of pentaerythritol
and 0.80 part of monobutyltin oxide. The content was stirred
while nitrogen gas was introduced. The temperature of the
content was elevated from 200°C to 240°C over a period of 6 hours
while water produced and part of the unreacted monomers were
removed, to carry out a reaction. Further, the reaction was
continued at 240°C for 3 hours while dehydration was carried out
under a reduced pressure of 50 mmHg. The thus-obtained polyester
had a weight average molecular weight of 43,000, an acid value
of 0.35 mgKOH/g and a hydroxyl value of 46 mgKOH/g.
Four kinds of white coating liquids were prepared by using
modified polymers A and B, produced in Examples 1 and 2, and
modified polymers E and G, produced in Comparative Examples 1
and 3, and polyester produced in Reference Example 1, according
to the formulations (parts by weight) shown in Table 6. The
ingredients shown in Table 6 were kneaded together by a sand
grinder mill for 1 hour, and each mixture was diluted with xylene
to give a coating liquid having a flowability of 13 to 14 seconds
as flowing down time.
| Examples | Comp. Examples | |||
| 9 | 10 | 7 | 8 | |
| Modified | ||||
| polymer A | 25 | - | - | - |
| Modified | ||||
| polymer B | - | 25 | - | - |
| Modified | ||||
| polymer E | - | - | 25 | - |
| Modified | ||||
| polymer G | - | - | - | 25 |
| Polyester | 20 | 20 | 20 | 20 |
| Titanium | 30 | 30 | 30 | 30 |
| oxide | ||||
| Xylene | 125 | 125 | 125 | 125 |
The above-mentioned plate X was washed with water, and then
dried. Each white coating liquid shown in Table 6 was applied
onto plate X by a spray coating method using the same spray gun
as mentioned to form a coating having a thickness of 40 µm. The
coating was dried at 23°C for 15 minutes and further at 80°C for
30 minutes in a non-circular drier. The dried coated plate was
allowed to stand for 7 days at room temperature, and then, was
tested for its initial adhesion (lattice pattern cutting test),
wet adhesion and accelerated weather resistance. The results
are shown in Table 7.
| Examples | Comp. Examples | |||
| 9 | 10 | 7 | 8 | |
| Initial adhesion | 100/100 | 100/100 | 90/100 | 90/100 |
| Wet adhesion | 100/100 | 100/100 | 60/100 | 50/100 |
| Accelerated | ||||
| weathering | ||||
| resistance (%) | ||||
| Exp. time 0 hr | 100 | 100 | 100 | 100 |
| 100 hr | 98 | 98 | 95 | 94 |
| 250 hr | 98 | 98 | 92 | 90 |
| 480 hr | 95 | 96 | 88 | 87 |
As seen the results of evaluation of coating liquids shown
in Table 7, the coating liquid comprising modified polymer A or
B of the present invention exhibits improved adhesion to an olefin
resin shaped article. In contrast, the coating liquid comprising
modified polymer G having a hydroxyl value of 140 mgKOH/g has
a poor wet adhesion.
Sampling was carried out according to the ink formulation
shown in Table 8. The prepared composition was kneaded by using
a twin-roll mill for 30 minutes, and was diluted with toluene
to an extent such that the flowing down time was 25 to 30 seconds
as measured at 20°C by a No. 3 Zahn-type flow cup, to prepare
a blue ink. As a pigment, copper phthalocyanine cyan pigment
Heriogen Blue S7084 (available from BASF AG) was used. The blue
ink was coated on a polypropylene film by a coating rod No. 14
(available from Tokyo Photoeletric Co.), and the coating layer
was dried at 23°C for 24 hours. The initial adhesion was evaluated
by the lattice pattern cutting test. The results are shown in
Table 8.
| Examples | Comp. Examples | |||
| 11 | 12 | 9 | 10 | |
| Modified | ||||
| polymer A | 30 | - | - | - |
| Modified | ||||
| polymer C | - | 30 | - | - |
| Modified | ||||
| polymer E | - | - | 30 | - |
| Modified | ||||
| polymer G | - | - | - | 30 |
| Polyester | 15 | 15 | 15 | 15 |
| Toluene | 120 | 120 | 120 | 120 |
| Cyan pigment | 5 | 5 | 5 | 5 |
| Initial | ||||
| adhesion | 100/100 | 100/100 | 30/100 | 90/100 |
| Heat seal | ||||
| strength | 270 | 250 | 80 | 150 |
| (g/cm) |
As seen from the results for evaluation of inks shown in
Table 8, the ink comprising modified polymer A or C of the present
invention exhibits improved adhesion to an olefin resin shaped
article. In contrast, the ink comprising modified polymer G
having a hydroxyl value of 140 mgKOH/g has a poor wet adhesion.
In the case when a shaped article, such as a resin shaped
article, especially an olefin resin shaped article primer, is
surface-treated with a primer (i.e., a kind of coating material)
comprising the modified polymer of the present invention, the
shaped article exhibits improved adhesion to and coatability with
a coating liquid or an adhesive. In the case when the modified
polymer of the present invention is incorporated as a binder resin
or vehicle in a coating material such as a coating liquid or an
ink, the coating material gives similarly adhesion-improving
effects. The coating material comprising the modified polymer
of the present invention exhibits improved adhesion to various
shaped articles, particularly a resin shaped article, especially
an olefin resin shaped article, and therefore, when the shaped
articles are coated with the coating material, its surface
appearance and texture can be kept for a long period of time.
In view of the above-mentioned beneficial effects, the
coating material comprising the modified polymer of the present
invention is suitable for use in surface modification of molding
parts such as automobile parts, and electrical and electronic
parts; packaging materials such as an adhesive tape; containers
for beverage and cosmetics; sports goods such as sport shoes and
golf balls; and construction materials and civil engineering
materials, including gaskets and sealing materials. The coating
material is especially useful for surface modification of
automobile exterior parts such as bumpers, mat guards, weather
strips and glass channels; and automobile interior parts such
as instrument panels, grommets and air-bags.
Claims (17)
- A modified polymer having a hydroxyl value in the range of 1 to 100 mgKOH/g, which is obtained by addition reaction of a compound (b) having one or more hydroxyl groups and a polymerizable unsaturated bond to a cyclized product (a) of a conjugated diene polymer having a cyclization degree in the range of 30 to 95%.
- The modified polymer according to claim 1, wherein the cyclized product of a conjugated diene polymer is a cyclized product of a homopolymer of a conjugated diene monomer or a copolymer of two or more kinds of conjugated diene monomers, or a copolymer of a conjugated diene monomer or monomers with not larger than 60% by weight of other copolymerizable monomer.
- The modified polymer according to claim 2, wherein the conjugated diene monomer is at least one monomer selected from 1,3-butadiene and isoprene.
- The modified polymer according to any one of claims 1 to 3, wherein the cyclized product of a conjugated diene polymer has a cyclization degree in the range of 50 to 90%.
- The modified polymer according to any one of claims 1 to 4, wherein the compound (b) having one or more hydroxyl groups and a polymerizable unsaturated bond is at least one compound selected from hydroxyalkyl esters of an unsaturated acid, unsaturated acid amides having one or more hydroxyl groups, polyalkylene glycol monoesters of an unsaturated acid, and polyhydric alcohol monoesters of an unsaturated acid.
- The modified polymer according to any one of claims 1 to 4, wherein the compound (b) having one or more hydroxyl groups and a polymerizable unsaturated bond is at least one compound selected from hydroxyalkyl esters of an unsaturated acid.
- The modified polymer according to any one of claims 1 to 4, wherein the compound (b) having one or more hydroxyl groups and a polymerizable unsaturated bond is at least one compound selected from 2-hydroxylethyl acrylate and 2-hydroxyethyl methacrylate.
- The modified polymer according to any one of claims 1 to 7, which has a hydroxyl value in the range of 5 to 50 mgKOH/g.
- The modified polymer according to any one of claims 1 to 8, which has a weight average molecular weight in the range of 5,000 to 600,000 as measured by gel permeation chromatography (GPC) and expressed in terms of that of polystyrene.
- A coating material comprising the modified polymer as described in any one of claims 1 to 9.
- The coating material according to claim 10, which is a primer, a coating liquid or an ink.
- The coating material according to claim 10, which is a primer comprising 5 to 95% by weight, based on the weight of the coating material, of the modified polymer.
- The coating material according to claim 10, which is a coating liquid comprising 5 to 95% by weight, based on the weight of the coating material, of the modified polymer.
- The coating material according to claim 10, which is an ink comprising a vehicle comprised of a polymer ingredient and a solvent wherein the polymer ingredient comprises 5 to 100% by weight of the modified polymer.
- A coated shaped article comprising a shaped article and a coating layer formed on the surface of the shaped article; said coating layer is formed from the coating material as claimed in any one of claims 10 to 14.
- The coated shaped article according to claim 15, wherein the shaped article is comprised of a polyolefin resin.
- A process for making a coated shaped article comprising coating the surface of a shaped article with the coating material as claimed in any one of claims 10 to 14.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002030084A JP3985139B2 (en) | 2002-02-06 | 2002-02-06 | Modified polymers and coating materials |
| JP2002030084 | 2002-02-06 | ||
| PCT/JP2003/001220 WO2003066694A1 (en) | 2002-02-06 | 2003-02-06 | Modified polymer and coating material |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1477501A1 true EP1477501A1 (en) | 2004-11-17 |
| EP1477501A4 EP1477501A4 (en) | 2006-04-05 |
| EP1477501B1 EP1477501B1 (en) | 2007-05-30 |
Family
ID=27677900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03737500A Expired - Lifetime EP1477501B1 (en) | 2002-02-06 | 2003-02-06 | Modified polymer and coating material |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20050209412A1 (en) |
| EP (1) | EP1477501B1 (en) |
| JP (1) | JP3985139B2 (en) |
| AT (1) | ATE363497T1 (en) |
| DE (1) | DE60314095T2 (en) |
| WO (1) | WO2003066694A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7964600B2 (en) | 2003-12-22 | 2011-06-21 | Memory Pharmaceuticals Corporation | Indoles, 1H-indazoles, 1,2-benzisoxazoles, and 1,2-benzisothiazoles, and preparation and uses thereof |
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|---|---|---|---|---|
| WO2003033255A1 (en) * | 2001-10-16 | 2003-04-24 | Zeon Corporation | Composite molding with adhesive composition layer comprising conjugated diene polymer having cyclic structure, and coating material |
| CN100415774C (en) * | 2003-01-23 | 2008-09-03 | 日本瑞翁株式会社 | Cyclized rubber containing polar groups and preparation method thereof |
| JP4569270B2 (en) * | 2003-12-04 | 2010-10-27 | 日本ゼオン株式会社 | Oxygen absorber |
| CA2567977A1 (en) * | 2004-04-22 | 2006-01-05 | Memory Pharmaceutical Corporation | Indoles, 1h-indazoles, 1,2-benzisoxazoles, 1,2-benzoisothiazoles, and preparation and uses thereof |
| US20080090042A1 (en) * | 2004-12-27 | 2008-04-17 | Zeon Corporation | Oxygen-Absorbing Multilayer Sheet, Packaging Material Comprising the Same and Packaging Container |
| JP4462033B2 (en) * | 2004-12-27 | 2010-05-12 | 日本ゼオン株式会社 | Oxygen-absorbing multilayer film, packaging material and packaging container comprising the same |
| CN100556688C (en) * | 2004-12-27 | 2009-11-04 | 日本瑞翁株式会社 | Oxygen-absorbing multilayer film, packaging material comprising same, and packaging container |
| JP4894276B2 (en) * | 2005-03-14 | 2012-03-14 | 住友化学株式会社 | Polyolefin resin composition |
| WO2006101021A1 (en) * | 2005-03-23 | 2006-09-28 | Zeon Corporation | Gas barrier resin composition having oxygen-absorbing property and gas barrier structure having oxygen-absorbing property including the same |
| US8293346B2 (en) * | 2005-03-23 | 2012-10-23 | Zeon Corporation | Oxygen absorbent and oxygen-absorbing multi-layer body |
| JP5082848B2 (en) * | 2005-05-31 | 2012-11-28 | 日本ゼオン株式会社 | Oxygen absorber, oxygen-absorbing film and packaging container |
| JP4946010B2 (en) * | 2005-05-31 | 2012-06-06 | 日本ゼオン株式会社 | Multi-layer plastic container |
| US20090119175A1 (en) * | 2007-11-07 | 2009-05-07 | John Richardson | Tape sealant |
| US20130289196A1 (en) | 2012-04-30 | 2013-10-31 | Shurtape Technologies, Llc | Film forming formulation for textured surfaces |
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| US3551242A (en) * | 1966-12-19 | 1970-12-29 | Phillips Petroleum Co | Unprocessed material utilization through selective contact |
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| JPS5996112A (en) * | 1982-11-26 | 1984-06-02 | Toyo Soda Mfg Co Ltd | Production of high-purity cyclized isoprene polymer |
| US4678841A (en) * | 1984-03-05 | 1987-07-07 | Kuraray Company, Ltd. | Method of producing a cyclized polydiene |
| JPS6128545A (en) * | 1984-07-18 | 1986-02-08 | Hitachi Ltd | Resin composition, laminate, and their preparation |
| JPS6286369A (en) * | 1985-10-11 | 1987-04-20 | Toppan Printing Co Ltd | Electrophotographic wet developer |
| JPH0753842B2 (en) * | 1986-07-16 | 1995-06-07 | 日本曹達株式会社 | Paint resin and method for producing the same |
| JP2580581B2 (en) * | 1987-01-28 | 1997-02-12 | 凸版印刷株式会社 | Wet developer |
| JPH0637530B2 (en) * | 1987-06-24 | 1994-05-18 | 日本ゼオン株式会社 | Novel optical material |
| EP0709413B1 (en) * | 1989-05-19 | 1999-07-14 | Japan Synthetic Rubber Co., Ltd. | (Modified) Hydrogenated diene block copolymer and composition comprising the same |
| JP3359080B2 (en) * | 1993-03-23 | 2002-12-24 | 東京応化工業株式会社 | Coating solution for forming acid-resistant protective film and method for manufacturing semiconductor device using the same |
| US5747597A (en) * | 1995-09-25 | 1998-05-05 | Dainippon Ink And Chemicals, Inc. | Curable resin composition and coating material composition |
| DE19602555A1 (en) * | 1996-01-25 | 1997-08-07 | Basf Lacke & Farben | Aqueous binder solutions and dispersions |
| US5919604A (en) * | 1997-07-30 | 1999-07-06 | Polyfibron Technologies, Inc. | Rubber-based aqueous developable photopolymers and photocurable elements comprising same |
| CN1246366C (en) * | 1999-02-10 | 2006-03-22 | 三洋化成工业株式会社 | Block polymer and antistatic agent comprising the same |
| DE19924340A1 (en) * | 1999-05-27 | 2000-11-30 | Basf Ag | Process for the selective hydrogenation of ethylenically unsaturated double bonds in polymers |
-
2002
- 2002-02-06 JP JP2002030084A patent/JP3985139B2/en not_active Expired - Fee Related
-
2003
- 2003-02-06 US US10/503,601 patent/US20050209412A1/en not_active Abandoned
- 2003-02-06 DE DE2003614095 patent/DE60314095T2/en not_active Expired - Lifetime
- 2003-02-06 WO PCT/JP2003/001220 patent/WO2003066694A1/en not_active Ceased
- 2003-02-06 EP EP03737500A patent/EP1477501B1/en not_active Expired - Lifetime
- 2003-02-06 AT AT03737500T patent/ATE363497T1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7964600B2 (en) | 2003-12-22 | 2011-06-21 | Memory Pharmaceuticals Corporation | Indoles, 1H-indazoles, 1,2-benzisoxazoles, and 1,2-benzisothiazoles, and preparation and uses thereof |
| US8158629B2 (en) | 2003-12-22 | 2012-04-17 | Memory Pharmaceuticals Corporation | Indoles, 1H-indazoles, 1,2-benzisoxazoles, and 1,2-benzisothiazoles, and preparation and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE60314095T2 (en) | 2008-01-31 |
| JP2003226722A (en) | 2003-08-12 |
| US20050209412A1 (en) | 2005-09-22 |
| EP1477501B1 (en) | 2007-05-30 |
| EP1477501A4 (en) | 2006-04-05 |
| ATE363497T1 (en) | 2007-06-15 |
| JP3985139B2 (en) | 2007-10-03 |
| WO2003066694A1 (en) | 2003-08-14 |
| DE60314095D1 (en) | 2007-07-12 |
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